EP1000070B1 - Silicon-containing chain extenders - Google Patents
Silicon-containing chain extenders Download PDFInfo
- Publication number
- EP1000070B1 EP1000070B1 EP98931847A EP98931847A EP1000070B1 EP 1000070 B1 EP1000070 B1 EP 1000070B1 EP 98931847 A EP98931847 A EP 98931847A EP 98931847 A EP98931847 A EP 98931847A EP 1000070 B1 EP1000070 B1 EP 1000070B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyurethane
- diisocyanate
- macrodiol
- chain extender
- radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004970 Chain extender Substances 0.000 title claims abstract description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 94
- 229920002635 polyurethane Polymers 0.000 claims abstract description 87
- 239000004814 polyurethane Substances 0.000 claims abstract description 87
- 150000002009 diols Chemical class 0.000 claims abstract description 22
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 15
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 9
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 9
- 125000005647 linker group Chemical group 0.000 claims abstract description 5
- -1 heterocycle radicals Chemical class 0.000 claims description 220
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims description 28
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229920000570 polyether Polymers 0.000 claims description 22
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 18
- 238000006731 degradation reaction Methods 0.000 claims description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 18
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 18
- 239000007943 implant Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- 125000000623 heterocyclic group Chemical group 0.000 claims description 14
- 125000002911 monocyclic heterocycle group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000002950 monocyclic group Chemical group 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 125000003367 polycyclic group Polymers 0.000 claims description 8
- 230000000747 cardiac effect Effects 0.000 claims description 7
- 229910052760 oxygen Chemical group 0.000 claims description 7
- OWJKJLOCIDNNGJ-UHFFFAOYSA-N 4-[[4-hydroxybutyl(dimethyl)silyl]oxy-dimethylsilyl]butan-1-ol Chemical compound OCCCC[Si](C)(C)O[Si](C)(C)CCCCO OWJKJLOCIDNNGJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012620 biological material Substances 0.000 claims description 6
- 238000001727 in vivo Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000001301 oxygen Chemical group 0.000 claims description 5
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 4
- 210000003709 heart valve Anatomy 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 4
- 230000002792 vascular Effects 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000004419 alkynylene group Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 claims description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000196 1,4-pentadienyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 claims description 2
- 125000006039 1-hexenyl group Chemical group 0.000 claims description 2
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 claims description 2
- 125000006023 1-pentenyl group Chemical group 0.000 claims description 2
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 claims description 2
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 claims description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000006041 3-hexenyl group Chemical group 0.000 claims description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 claims description 2
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 claims description 2
- 101100331550 Antirrhinum majus DICH gene Proteins 0.000 claims description 2
- 241001631457 Cannula Species 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000005035 acylthio group Chemical group 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000006323 alkenyl amino group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 claims description 2
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000006319 alkynyl amino group Chemical group 0.000 claims description 2
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000005251 aryl acyl group Chemical group 0.000 claims description 2
- 125000001769 aryl amino group Chemical group 0.000 claims description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 2
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000008280 blood Substances 0.000 claims description 2
- 210000004369 blood Anatomy 0.000 claims description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000012377 drug delivery Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 2
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 2
- 125000005292 haloalkynyloxy group Chemical group 0.000 claims description 2
- 125000003106 haloaryl group Chemical group 0.000 claims description 2
- 125000004996 haloaryloxy group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000002649 leather substitute Substances 0.000 claims description 2
- 238000005065 mining Methods 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 2
- 125000004999 nitroaryl group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 210000004872 soft tissue Anatomy 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000306 component Substances 0.000 claims 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 238000000034 method Methods 0.000 description 21
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- 238000012360 testing method Methods 0.000 description 12
- 230000035882 stress Effects 0.000 description 11
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 9
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- 239000003054 catalyst Substances 0.000 description 7
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- 239000010408 film Substances 0.000 description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 3
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 239000011995 wilkinson's catalyst Substances 0.000 description 2
- AHPRMFFBUKVDHZ-UHFFFAOYSA-N 5-[[5-hydroxypentyl(dimethyl)silyl]oxy-dimethylsilyl]pentan-1-ol Chemical compound OCCCCC[Si](C)(C)O[Si](C)(C)CCCCCO AHPRMFFBUKVDHZ-UHFFFAOYSA-N 0.000 description 1
- IOSZAJFVMXYBPJ-UHFFFAOYSA-N 6-[[6-hydroxyhexyl(dimethyl)silyl]oxy-dimethylsilyl]hexan-1-ol Chemical compound OCCCCCC[Si](C)(C)O[Si](C)(C)CCCCCCO IOSZAJFVMXYBPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- 239000012766 organic filler Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 206010033675 panniculitis Diseases 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4858—Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
Definitions
- the present invention generally relates to silicon-containing chain extenders and their use in the preparation of polyurethane elastomeric compositions having improved properties. These polyurethane compositions are useful for a variety of applications, in particular the manufacture of medical devices, articles or implants which contact living tissues or bodily fluids.
- Polyurethane elastomers are amongst the best performing synthetic polymers in medical implant applications. Their excellent mechanical properties coupled with relatively good biostability make them the choice materials for a number of medical implants including cardiac pacemakers, catheters, implantable prostheses, cardiac assist devices, heart valves and vascular grafts. The excellent mechanical properties of polyurethane elastomers are attributed to their two phase morphology resulting from microphase separation of soft and hard segments.
- the soft segment is typically formed from a polyether macrodiol such as poly(tetramethylene oxide) (PTMO) while the hard segment is derived from a diisocyanate such as 4,4'-methylenediphenyl diisocyanate (MDI) and a diol chain extender such as 1,4-butanediol (BDO).
- PTMO poly(tetramethylene oxide)
- MDI 4,4'-methylenediphenyl diisocyanate
- BDO 1,4-butanediol
- the diol chain extender which is used to link up diisocyanates is a relatively small difunctional molecule of molecular weight between about 60 and 350.
- the structure of the chain extender makes a significant contribution to the physical properties of the polyurethane elastomers.
- the most commonly used diol chain extender is 1,4-butanediol.
- polyurethane elastomers for applications such as cardiac pacemakers, in some cases the polyurethanes biodegrade causing surface or deep cracking, stiffening, erosion or the deterioration of mechanical properties such as flexural strength'. Elastomers with high flexibility and low Shore A Durometer hardness in particular degrade faster than the harder and more rigid grades. It is generally hypothesized that the degradation is primarily an in vivo oxidation process involving the polyether soft segment.
- the currently used medical polyurethanes are polyether-based and the most vulnerable site for degradation is the methylene group alpha to the ether oxygen 2 of the soft segment. Polyurethanes prepared with a lower amount of polyether component generally exhibit improved degradation resistance. However, such materials typically have high elastic modulus and are difficult to process making them less desirable for many implant applications. Pinchuk has recently reviewed the biostability of polyurethanes 3 .
- Non-PTMO based polyurethane formulations which show significantly improved in vivo degradation resistance as demonstrated by animal implant experiments have also recently been disclosed in the patent literature. These include polyurethane formulations based on polycarbonate macrodiols disclosed in US 5,133,742 (Pinchuk) and US 5,254,662 (Szycher) and polyether macrodiols with fewer ether linkages in US 4,875,308 (Meijs et al ). The aforementioned patents do not disclose polyurethane formulations which provide materials having flexural modulus, hardness and biostability comparable to those of silicon rubber while retaining high tensile strength, abrasion resistance and tear strength of typical polyurethane elastomers.
- compositions disclosed in US 5,254,662 provide materials with low elastic modulus and high tensile strength, since those compositions are based on polycarbonate macrodiols and aliphatic diisocyanates, their degradation resistance under in vivo conditions is questionable.
- Hergenrother et al 4 have demonstrated by animal implant experiments that aliphatic diisocyanate based polyurethanes degrade more than the aromatic diisocyanate based polyurethanes.
- non-PTMO based polyurethane elastomers address the issue of biostability, they do not provide methods of formulating polyurethanes having properties such as flexibility and biostability comparable to those of silicone rubber.
- the formulations disclosed in the above patents typically have hardness in excess of Shore 80 A.
- polyurethanes having properties such as low durometer hardness, low flexural modulus, good processability and high resistance to degradation, without the disadvantages of silicone rubber such as poor tensile strength, abrasion resistance and tear strength.
- Such polyurethanes should also preferably have a good biostability for applications such as pacemaker leads, vascular grafts, heart valves and the like.
- the present invention also provides use of the diol of the formula (I) defined above as a chain extender.
- the present invention further provides the diol of the formula (I) as defined above when used as a chain extender.
- the hydrocarbon radical for substituents R 1 , R 2 , R 3 and R 4 may include alkyl, alkenyl, alkynyl, aryl or heterocyclyl radicals. It will be appreciated that the equivalent radicals may be used for substituents R 5 , R 6 and R 7 except that the reference to alkyl, alkenyl and alkynyl should be to alkylene, alkenylene and alkynylene, respectively. In order to avoid repetition, only detailed definitions of alkyl, alkenyl and alkynyl are provided hereinafter.
- alkyl denotes straight chain, branched or mono- or poly-cyclic alkyl, preferably C 1-12 alkyl or cycloalkyl.
- straight chain and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-di
- cyclic alkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.
- alkenyl denotes groups formed from straight chain, branched or mono- or poly-cyclic alkenes including ethylenically mono- or polyunsaturated alkyl or cycloalkyl groups as defined above, preferably C 2-12 alkenyl.
- alkenyl examples include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3 heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decanyl, 3-decenyl, 1,3-butadienyl, 1,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrien
- alkynyl denotes groups formed from straight chain, branched, or mono- or poly-cyclic alkynes.
- alkynyl include ethynyl, 1-propynyl, 1- and 2-butynyl, 2-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 10-undecynyl, 4-ethyl-1-octyn-3-yl, 7-dodecynyl, 9-dodecynyl, 10-dodecynyl, 3-methyl-1-dodecyn-3-yl, 2-tridecynyl, 11-tridecynyl, 3-tetradecynyl, 7-hexadecynyl, 3-octadecynyn
- aryl denotes single, polynuclear, conjugated and fused residues of aromatic hydrocarbons.
- aryl include phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl and the like.
- heterocyclyl denotes mono- or poly-cyclic heterocyclyl groups containing at least one heteroatom selected from nitrogen, sulphur and oxygen.
- Suitable heterocyclyl groups include N-containing heterocyclic groups, such as, unsaturated 3 to 6 membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, for example, pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl or tetrazolyl; saturated 3 to 6-membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, such as pyrrolidinyl, imidazolidinyl, piperidino or piperazinyl; unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, such as, indolyl, isoindolyl, indolizinyl,
- optionally substituted means that a group may or may not be further substituted with one or more groups selected from oxygen, nitrogen, sulphur, alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carboxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, azido, amino, alkylamino, alkenylamino, alkynylamino, arylamino, benzylamino, acyl, alkenylacyl, alkynylacyl, alkenyl
- Suitable divalent linking groups for R 7 include O, S and NR wherein R is hydrogen or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical.
- Preferred silicon-containing diols are 1,3-bis(4-hydroxybutyl)tetramethyl disiloxane (compound of formula (I) wherein R 1 , R 2 , R 3 and R 4 are methyl, R 5 and R 6 are butyl and R 7 is O), 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene (compound of formula (I) wherein R 1 , R 2 , R 3 and R 4 are methyl, R 5 and R 6 are propyl and R 7 is ethylene) and 1,4-bis(3-hydroxypropyl)tetramethyl disiloxane.
- the silicon-containing diol chain extenders can be conveniently prepared by methods reported in the literature 6 . Some of these compounds such as 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene (HTDE) and 1,3-bis(4-hydroxybutyl) tetramethyl disiloxane (BHTD) are available commercially. Others can be prepared by using hydrosilylation reaction of the appropriate hydroxy alkene and 1,1,3,3,-tetramethyldisiloxane using a catalyst such as Wilkinson's catalyst.
- HTDE 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene
- BHTD 1,3-bis(4-hydroxybutyl) tetramethyl disiloxane
- Others can be prepared by using hydrosilylation reaction of the appropriate hydroxy alkene and 1,1,3,3,-tetramethyldisiloxane using a catalyst such as Wilkinson's catalyst.
- the present invention also provides a silicon-containing diol of the formula (I) defined above wherein R 7 is ethylene and n is 1 or 2.
- the diol of the formula (I) defined above is combined with a chain extender known in the art of polyurethane manufacture.
- a chain extender composition including a silicone-containing diol of the formula (I) defined above and a chain extender known in the art of polyurethane manufacture.
- the present invention also provides use of the composition defined above as a chain extender.
- the present invention further provides the composition defined above when used as a chain extender.
- the chain extender known in the art of polyurethane manufacture is preferably selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, p-xylene glycol and 1,4-bis(2-hydroxyethoxy) benzene. 1,4 butanediol is particularly preferred.
- the silicon chain extender and the known chain extender can be used in a range of molar proportions with decreasing tensile properties as the molar percentage of the silicon chain extender increases in the mixture.
- a preferred molar percentage of silicon chain extender is about 1 to about 50%, more preferably about 40%.
- the preferred chain extender composition contains one known chain extender and one silicon-containing diol, it will be understood that mixtures containing more than one known chain extender and diol may be used in the chain extender composition.
- the chain extender and chain extender composition of the present invention are particularly useful in preparing polyurethane elastomeric compositions.
- a polyurethane elastomeric composition which includes a chain extender or chain extender composition defined above.
- the polyurethane elastomeric compositions of the present invention may be prepared by any suitable known technique.
- a preferred method involves mixing the chain extender or chain extender composition with a soft segment macrodiol and then reacting this mixture with a diisocyanate.
- the initial ingredients are preferably mixed at a temperature in the range of about 45 to about 100°C, more preferably about 60 to about 80°C.
- a catalyst such as dibutyl tin dilaurate at a level of about 0.001 to about 0.5 wt % based on the total ingredients may be added to the initial mixture.
- the mixing may occur in conventional apparatus or within the confines of a reactive extruder or continuous reactive injection molding machine.
- the polyurethanes may be prepared by the prepolymer method which involves reacting a diisocyanate with the soft segment macrodiol to form a prepolymer having terminal reactive diisocyanate groups. The prepolymer is then reacted with the chain extender or chain extender composition.
- polyurethane elastomeric composition of the present invention may be further defined as comprising a reaction product of:
- the soft segment macrodiol may be of any suitable type known in the art of polyurethane manufacture. Examples include polyethers, polyesters, polysiloxanes, polycarbonates or mixtures thereof. Preferably, the soft segment is derived from a polysiloxane macrodiol and a polyether macrodiol.
- a suitable polysiloxane is polydimethyl siloxane (PDMS).
- PDMS polydimethyl siloxane
- the polysiloxane macrodiols may be obtained as commercially available products such as X-22-160AS from Shin Etsu or prepared according to known procedures 7 .
- the preferred molecular weight range of the polysiloxane macrodiol is about 200 to about 5000, preferably about 300 to about 1200.
- Suitable polyether macrodiols include those represented by the formula (II) HO -[( CH 2 ) m - O ] n - H (II) wherein
- polyether macrodiols such as PTMO
- the more preferred macrodiols and their preparation are described in Gunatillake et al 8 and US 5403912.
- Polyethers such as PHMO described in these references are more hydrophobic than PTMO and are more compatible with polysiloxane macrodiols.
- the preferred molecular weight range of the polyether macrodiol is about 200 to about 5000, more-preferably about 200 to about 1200.
- the diisocyanate is selected from 4,4'-methylenediphenyl diisocyanate (MDI), methylene bis (cyclohexyl) diisocyanate (H12MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1, 4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (DICH), 2,4-toluene diisocyanate (2,4-TDI) or its isomers or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI) and m-tetramethylxylene diisocyanate (m-TMXDI). MDI is particularly preferred.
- MDI 4,4'-methylenediphenyl diisocyanate
- H12MDI methylene bis (cyclohexyl) diisocyanate
- p-PDI
- a particularly preferred polyurethane elastomeric composition of the present invention comprises a reaction product of:
- the silicon chain extender is present in an amount of about 40 mol % of the chain extender composition.
- the polyurethane may be processed by conventional methods such as extrusion, injection and compression moulding without the need of added processing waxes.
- conventional polyurethane processing additives such as catalysts, antioxidants, stablisers, lubricants, dyes, pigments, inorganic and/or organic fillers and reinforcing materials can be incorporated into the polyurethane during preparation.
- additives are preferably added to the soft segment macrodiol.
- the soft segment macrodiol, diisocyanate and the chain extender or chain extender composition may be present in certain preferred proportions.
- the preferred level of hard segment (i.e. diisocyanate and chain extender) in the composition is about 40 to about 60 wt%.
- the weight ratio of polysiloxane to polyether in the preferred soft segment may be in the range of from 1:99 to 99:1.
- a particularly preferred ratio of polysiloxane to polyether which provides increased degradation resistance, stability and clarity is 80:20.
- the polyurethane elastomeric composition of the present invention is particularly useful in preparing materials having good mechanical properties, in particular biomaterials.
- a material having improved mechanical properties, clarity, processability and/or degradation resistance comprising a polyurethane elastomeric composition which includes a chain extender or chain extender composition defined above.
- the present invention also provides use of the polyurethane elastomeric composition defined above as a material having improved mechanical properties, clarity, processability and/or degradation resistance.
- the present invention further provides the polyurethane elastomeric composition defined above when used as a material having improved mechanical properties, clarity, processability and/or degradation resistance.
- the mechanical properties which are improved include tensile strength, tear strength, abrasion resistance, Durometer hardness, flexural modulus and related measures of flexibility or elasticity.
- the improved resistance to degradation includes resistance to free radical, oxidative, enzymatic and/or hydrolytic processes and to degradation when implanted as a biomaterial.
- the improved processability includes ease of processing by casting such as solvent casting and by thermal means such as extrusion and injection molding, for example, low tackiness after extrusion and relative freedom from gels.
- the polyurethane elastomeric composition of the present invention shows good elastomeric properties. It should also have a good compatibility and stability in biological environments, particularly when implanted in vivo for extended periods of time.
- an in vivo degradation resistant material which comprises the polyurethane elastomeric composition defined above.
- the polyurethane elastomeric composition may also be used as a biomaterial.
- biomaterial is used herein in its broadest sense and refers to a material which is used in situations where it comes into contact with the cells and/or bodily fluids of living animals or humans.
- the polyurethane elastomeric composition is therefore useful in manufacturing medical devices, articles or implants.
- the present invention still further provides medical devices, articles or implants which are composed wholly or partly of the polyurethane elastomeric composition defined above.
- the medical devices, articles or implants may include cardiac pacemakers, defibrillators and other electromedical devices, catheters, cannulas, implantable prostheses, cardiac assist devices, heart valves, vascular grafts, extra-corporeal devices, artificial organs, pacemaker leads, defibrillator leads, blood pumps, balloon pumps, A-V shunts, biosensors, membranes for cell encapsulation, drug delivery devices, wound dressings, artificial joints, orthopaedic implants and soft tissue replacements.
- polyurethane elastomeric compositions having properties optimised for use in the construction of various medical devices, articles or implants will also have other non-medical applications.
- Such applications may include their use in the manufacture of artificial leather, shoe soles; cable sheathing; varnishes and coatings; structural components for pumps, vehicles, etc; mining ore screens and conveyor belts; laminating compounds, for example in glazing; textiles; separation membranes; sealants or as components of adhesives.
- the present invention extends to the use of the polyurethane elastomeric composition defined above in the manufacture of devices or articles.
- the present invention also provides devices or articles which are composed wholly or partly of the polyurethane elastomeric composition defined above.
- PHMO Poly(hexamethylene oxide)
- PHMO Poly(hexamethylene oxide)
- a mixture of dried PDMS (260.0 g), PHMO (65.00 g), 1,4-butanediol (16.14 g), dibutyl tin dilaurate catalyst (0.054 g), Irgawax (0.81 g) and Irganox 1010 (0.54 g) was placed into a 1L flask and degassed at 80°C for 2 h under vacuum (0.2 torr). Separately degassed BHTD (33.256 g) was added to the flask containing the macrodiol mixture. This mixture (370.00 g) was weighed into a 1L polypropylene beaker and allowed to cool to 70°C under nitrogen.
- Molten MDI (164.67 g) at 60°C was weighed in a fume hood into 250 ml polypropylene beaker. The MDI was then quickly added with rapid stirring using a stainless steel spatula. The mixture, which was initially cloudy, turned clear with mixing after about 10 sec. The viscous mixture was rapidly poured onto a teflon coated metal tray and cured in an oven under nitrogen at 100°C. Heating was discontinued after 4 h and the sheet of polyurethane was allowed to cool to ambient temperature over a period of about 15 h.
- the degradation resistance of the polyurethane composition described in example 1 was examined by a three month ovine implant experiment.
- Polyurethane in example 1, Pellethane 2363-80A (Registered Trade Mark) and 2363-55D were compression moulded into sheets of 0.5 mm thickness. Specimens shaped as dumbbells were cut from the sheets and stretched over poly(methyl methacrylate) holders. This caused the central section to be strained to 250% of its original length. A polypropylene suture was firmly tied around the centre of each specimen. This caused a localised increase in stress in the specimen. The specimens attached to their holders were sterilised with ethylene oxide and implanted into the subcutaneous adipose tissue in the dorsal thoraco-lumbar region of adult crossbred wether sheep. This test method provides a means of assessing the resistance to biodegradation by environmental stress cracking.
- the thermal processability of the polyurethane elastomer prepared according to the procedure in example 1 was evaluated by extrusion into a thin film (0.5 mm) using a single screw Brabender extruder.
- the polyurethane was dried at 45°C under vacuum (0.1 torr) for 48 h prior to the extrusion.
- a polyurethane composition based on a mixture of PDMS/PHMO, a mixture of BDO and BHTD, and MDI was prepared by a two-step bulk polymerisation procedure without the use of the catalyst or other conventional additives used in example 1.
- the composition was based on an isocyanate index ([NCO/[OH]) of 1.03 and a hard segment weight percentage of 40.
- PDMS (Shin Etsu product X-22-160AS, MW 937.83) was dried at 105°C for 15h under vacuum (0.1 torr).
- PHMO (MW 696.06) was dried at 130°C under vacuum (0.1 torr) for 4 h prior to polymerisation.
- Molten MDI (195.0 g) was weighed into a 2 L three necked round bottom flask fitted with an additional funnel, nitrogen inlet and a mechanical stirrer.
- the dried polyol mixture 240.0 g PDMS and 60.0 g PHMO
- the reaction temperature was maintained at 70°C.
- the reaction was continued for further 2 h at 80°C with stirring to form the prepolymer.
- the prepolymer (537.1 g) was then weighed into a 2 L polypropylene beaker and thoroughly mixed with the chain extenders BDO (16.82 g) for 2 min.
- the polymer was poured into a teflon coated pan and cured at 100°C for 4 h in an oven under nitrogen.
- the cured polyurethane after drying at 45°C under vacuum (0.1 torr) was compression moulded at 180°C into 2 mm thick flat sheets for testing tensile properties and flexural modulus, and 2 mm thick, 10.5 cm diameter discs for abrasion resistance.
- Tensile properties and flexural strength were tested on an Instron Model 4032 Universal Testing Machine while the abrasion resistance was tested on a Taber Model 503 Abraser using Calibrade H-22 abrading wheels and 1000 g wheel loading.
- the tensile test specimens were 10 cm long dumbbells with a 6 mm wide narrow section.
- Table 2 The test results are summarised in Table 2 along with corresponding properties for a commercial sample of silicon rubber. Some properties of high tear strength silicon rubber as reported in the literature 5 are shown in Table 3 for comparison.
- HTDE 1,4-bis(3-hydroxypropyl)-1,1,4,4-tetramethyl disilylethylene
- 1,1,4,4,-Tetramethyldisilylethylene (50.0 g) and tris(triphenylphosphine) rhodium chloride (Wilkinson's catalyst, 0.005 g) were placed in a 500 ml round bottom flask fitted with a nitrogen inlet, addition funnel, a drying tube and a condenser. The flask was placed in an oil bath at 40°C and allylalcohol (80.00 g) was added to the reaction mixture over a period of 30 min. After the addition was completed, the oil bath temperature was raised to 80°C and continued reaction for 2 h. A sample of the reaction was analysed by IR spectroscopy.
- PDMS and PHMO were purified according to the procedures described in Example 1. PDMS (28.00 g), PHMO (7.00 g), BDO (2.433 g), HTDE (2.363 g) and dibutyl tin dilauarate (0.006 g) were weighed into a 100 ml poly(propylene) beaker and degassed at 80°C for 2 h under vacuum (2 torr). Molten MDI (18.57 g) was quickly added to the contents in the beaker and stirred rapidly. The polymer was cured in the beaker at 100°C for 4 h in an oven under nitrogen.
- BHPD 1,3-bis(5-hydroxypentyl)-1,1,3,3-tetramethyldisiloxane
- BHHD 1,3-bis(6-hydroxyhexyl)-1,1,3,3-tetramethyldisiloxane
- Two polyurethanes were prepared using a one step procedure similar to that described in example 1.
- the polyurethane based on BHPD was prepared from PDMS (20.0 g), PHMO (5.0 g), MDI (12.72 g), BDO (1.209 g), BHPD (2.742 g) and catalyst dibutyl tin dilaurate (0.004 g).
- a polyurethane based on BHHD was prepared from PDMS (20.0 g), PHMO (5.0 g), MDI (12.57 g), BDO (1.178 g), BHHD (2.914 g) and dibutyl tin dilaurate (0.004 g).
- PDMS and PHMO were purified according to the procedures described in Example 1.
- PDMS (5.00 g), PHMO (20.0 g), BDO (2.04 g), BHTD (4.203 g) and dibutyl tin dilaurate (0.005 g) were weighed into a 100 ml poly(propylene) beaker and degassed at 80°C for 2 h under vacuum (2 torr).
- Hydrogenated MDI Aldrich, 18.76 g was quickly added to the contents in the beaker and stirred rapidly. The polymer was cured in the beaker at 100°C for 4 h in an oven under nitrogen.
- the polymer after curing was colourless and transparent.
- a 1 mm thick sheet of the polymer was prepared by compression moulding at 180°C. Dumbbells punched from the sheet were tested for tensile properties on an Instron Model 4032 Universal Testing Machine: fail stress 18 MPa, fail strain 410%, stress at 100% elongation 2.3 MPa, Young's modulus 10 MPa and Shore hardness 60A.
- This example illustrates the synthesis of a polyurethane composition using a PDMS macrodiol with a molecular weight of 1913.3 according to a two-step polymerisation procedure.
- MDI (23.85g) was weighed into a 250mL three necked round bottom flask fitted with a dry nitrogen inlet, a mechanical stirrer and an addition funnel.
- the reaction flask was placed in an oil bath at 70°C and the polyol mixture (40.00g, PDMS molecular weight 1913.3 and 10.00g PHMO, molecular weight 700.16) was slowly added to MDI from the addition funnel over a period of 15 min. After completion of the addition, the oil bath temperature was raised to 80°C and reacted for 2 hours with stirring under a slow flow of nitrogen to complete the reaction.
- the prepolymer was then dissolved in anhydrous N,N-dimethyformamide (DMF) (440mL) to make a 15% solution.
- DMF N,N-dimethyformamide
- the chain extender mixture 1,4-butanediol (3.099g) and 1,3bis(4-hydroxybutyl)tetramethyl disiloxane (6.387g), was added to the prepolymer solution and reacted at 90°C for 4h with stirring.
- a 0.5mm thick film was cast from the DMF solution of the polymer onto a Petrie dish and dried at 45°C in an over for 48h to remove the solvent. The cast film was clear and transparent. Test specimens were punched from the film for testing tensile properties and tear strength.
- the polyurethane exhibited 22 MPa fail stress, 440% fail strain, 15 MPa Young's modulus, and 7 MPa stress at 100% elongation.
- the tear strength of the polyurethane was 60 N/mm.
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Dermatology (AREA)
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Applications Claiming Priority (3)
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| AUPO787897 | 1997-07-14 | ||
| AUPO7878A AUPO787897A0 (en) | 1997-07-14 | 1997-07-14 | Silicon-containing chain extenders |
| PCT/AU1998/000546 WO1999003863A1 (en) | 1997-07-14 | 1998-07-14 | Silicon-containing chain extenders |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1000070A1 EP1000070A1 (en) | 2000-05-17 |
| EP1000070A4 EP1000070A4 (en) | 2000-06-07 |
| EP1000070B1 true EP1000070B1 (en) | 2003-09-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP98931847A Expired - Lifetime EP1000070B1 (en) | 1997-07-14 | 1998-07-14 | Silicon-containing chain extenders |
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| US (1) | US6420452B1 (pt) |
| EP (1) | EP1000070B1 (pt) |
| JP (1) | JP2001510196A (pt) |
| CN (1) | CN1267304A (pt) |
| AT (1) | ATE249466T1 (pt) |
| AU (2) | AUPO787897A0 (pt) |
| BR (1) | BR9811689A (pt) |
| CA (1) | CA2296642C (pt) |
| DE (1) | DE69818063T2 (pt) |
| WO (1) | WO1999003863A1 (pt) |
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| DE4008259A1 (de) * | 1990-03-15 | 1991-09-19 | Bayer Ag | Siloxanmodifizierte thermoplastische polyurethane |
| JPH0425580A (ja) | 1990-05-22 | 1992-01-29 | Toyoda Gosei Co Ltd | 塗料組成物及び塗装体 |
| JPH082911B2 (ja) | 1990-06-06 | 1996-01-17 | 信越化学工業株式会社 | １，３―ビス（ｐ―ヒドロキシベンジル）―１，１，３，３―テトラメチルジシロキサン及びその製造方法 |
| NZ238807A (en) * | 1990-07-05 | 1994-03-25 | Merrell Dow Pharma | Bis[4-(2,6-dialkyl)phenol]silane derivatives and antiatherosclerotic compositions |
| US5330840A (en) * | 1992-05-28 | 1994-07-19 | Eastman Kodak Company | Polysiloxane containing polyurethane and coated articles useful as toner fusing members |
| US5239037A (en) * | 1992-07-16 | 1993-08-24 | Surface Coatings, Inc. | Waterproof breathable polyurethane membranes and porous substrates protected therewith |
| AUPO251096A0 (en) * | 1996-09-23 | 1996-10-17 | Cardiac Crc Nominees Pty Limited | Polysiloxane-containing polyurethane elastomeric compositions |
-
1997
- 1997-07-14 AU AUPO7878A patent/AUPO787897A0/en not_active Abandoned
-
1998
- 1998-07-14 AU AU82013/98A patent/AU748318B2/en not_active Ceased
- 1998-07-14 DE DE69818063T patent/DE69818063T2/de not_active Expired - Fee Related
- 1998-07-14 CA CA002296642A patent/CA2296642C/en not_active Expired - Fee Related
- 1998-07-14 BR BR9811689-4A patent/BR9811689A/pt not_active Application Discontinuation
- 1998-07-14 CN CN98808257A patent/CN1267304A/zh active Pending
- 1998-07-14 AT AT98931847T patent/ATE249466T1/de not_active IP Right Cessation
- 1998-07-14 JP JP2000503086A patent/JP2001510196A/ja active Pending
- 1998-07-14 WO PCT/AU1998/000546 patent/WO1999003863A1/en active IP Right Grant
- 1998-07-14 EP EP98931847A patent/EP1000070B1/en not_active Expired - Lifetime
-
2000
- 2000-01-14 US US09/483,165 patent/US6420452B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU748318B2 (en) | 2002-05-30 |
| DE69818063D1 (de) | 2003-10-16 |
| EP1000070A4 (en) | 2000-06-07 |
| CA2296642C (en) | 2005-11-08 |
| DE69818063T2 (de) | 2004-06-03 |
| CA2296642A1 (en) | 1999-01-28 |
| AUPO787897A0 (en) | 1997-08-07 |
| AU8201398A (en) | 1999-02-10 |
| JP2001510196A (ja) | 2001-07-31 |
| WO1999003863A1 (en) | 1999-01-28 |
| EP1000070A1 (en) | 2000-05-17 |
| ATE249466T1 (de) | 2003-09-15 |
| US6420452B1 (en) | 2002-07-16 |
| CN1267304A (zh) | 2000-09-20 |
| BR9811689A (pt) | 2000-09-26 |
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